Emulsions for warp sizing containing cationic hydroxyacetate



2,757,097 Patented July 31, 1956 EMULSIONS FOR WARP SIZING CONTAINING CATIONIC HYDROXY'ACETATE Roland Z. Farkas, Greenville, S. C., assignor to Texize Chemicals, Inc., Greenville, S. C., a corporation of South Carolina No Drawing. Application February 24, 1953, Serial No. 338,551

15 Claims. (Cl. 106-139) This invention relates to emulsifying agents and emulsions, and to methods for their production and utilization. The invention is particularly concerned with cationic protein emulsifying agents and emulsions for textile sizing, especially warp sizing, although the invention finds other applications as well.

The process of weaving yarn necessitates keeping the warp yarns under considerable tension and subjects them to the abrasive action of the heddles and and other movable parts of the loom. To prevent excessive breakage due to abrasion and to assure maximum production, the warp yarns as delivered on a warp beam to the slasher have to be sized. The principal ingredient of warp sizing is an adhesive stiffener, usually a starch. Starch sizes the individual threads and surrounds them with a tough film for protection against abrasion. Starch films alone, however, are too brittle and as such do not produce maximum weaving efficiency. Therefore, softeners, lubricants and binders are added to the starch solution to produce a more suitable and flexible size mixture.

Softeners include various vegetable, animal and mineral fats, oils, and waxes, which may also act as lubricants. l Resinous substances, such as oil modified alkyd resins and i hydroabietyl alcohol, may also be used as softeners.

Other lubricants include glycerin and diethylene glycol. Binders include various proteinaceous substances and gums. The gums may also be used as stitfeners to replace all or part of the starch. I The warp yarns are wound on a Warp beam, and several of these warp beams are simultaneously run into a hot starch solution modified with the lubricants, sof teners and binders. When they emerge, the yarns are dried on rotary steam cylinders, where the size ingredients are converted to insoluble form, and the yarns are wound on loom beams, to ready them for the weaving operation. An important factor in sizing materials is penetration. Penetration is aided to a considerable extent through the use of dispersing and emulsifying agents. It has been found advantageous to have the size ingredients in emulsion and well-dispersed throughout the size bath; and to this end, colloid mills and homogenizers are now in Widespread use. a Heretofore, various dispersions and emulsions have been employed for distributingthe insoluble content of size baths. In some cases, the ingredients for addition to starch solution are simple mixtures which are mechanically dispersed in the size bath. At times, the fats are partly saponified, and fatty, soapy mixtures are produced in paste form, for later addition to starch solution or slurry. Also, sulfated oils or fats are mixed with raw oils'or fats to produce water soluble products, and the mixtures are added to starch solutions. Fatty emulsions are also supplied, such as those prepared employing as emulsifying agents polyoxyethylene condensates of alcohols, fatty acids, fatty'amides and fatty amines, or amine condensates of fatty acids and fatty gycerides.

The mechanical mixtures do not meet the need for a water dispersible composition which will completely mix with a cold starch slurry in homogenizer operation. The various solubilized and emulsified compositions previously used are deficient in several respects: regulation of the moisture pickup of the yarn is difficult, foam is hard to control, and weaving efficiency of the resulting sized yarns is low.

Different mills have dilferent water and operating conditions. Under these variable conditions, a size ingredient such as the starch or added binders and softeners may cause foaming during the sizing operations, which lead to uneven sizing and waste of material; or due to their operating conditions, an insufficient amount of water in the form of moisture pick-up is present in the sized yarn. In such situations, salts are added to correct the foaming condition or to increase the moisture pick-up during weaving operations. The salts are hygroscopic in nature and tend to harden otherwise soft Water to produce a nonfoaming and yet more hygroscopic size mix. Illustrative of the salts employed are zinc and calcium chlorides and sulfates, alkali metal acetates, and urea salts.

Of the prior solubilized and emulsified compositions, the saponified products considerably increase the amount of foam produced. The addition of calcium or zinc chlorides or sulfates adversely affects the saponification and therefore is to be avoided, resulting in a product that will foam when mixed with starch. Anionic emulsifying agents are affected by the salts in the same manner. Nonionic emulsifying agents cannot be properly defoamed Without destroying the usefulness of the product itself for warp sizing.

The sulfated oils and fats, which are usually sodium alkyl sulfates, form zinc or calcium alkyl sulfates, thereby breaking the combinations of sulfated and raw oils or fats. Thus, the prior water dispersible products do not lend themselves to eflicieut operation and the production of products of the desired quality.

This invention is concerned with the discovery that cationic proteins are valuable emulsifying agents, and that superior emulsions overcoming the disadvantages of the prior compositions can be produced employing cationic proteins. The new emulsions are very advantageously employed in warp sizing operations, which is particularly surprising, inasmuch as this appears to be the first use of cationic protein emulsions in textile sizing. They find application in warp sizing cellulosic and synthetic spun fibers, including nylon, Orlon and Dacron. The use of cationic proteins is not confined to sizing emulsions, however, but extends to the preparation of other emulsions with emulsifiable substances, such as resins, pigments and rubbers, for example.

The new cationic protein emulsifying agents are preferably cationic protein hydroxyacetates or cationic protein oxydiacetate s, prepared from protein and .hydroxyacetic acid (glycolic acid) or oxydiacetic acid (diglycolic acid). While the invention will be described with particular reference to hydroxyacetic acid and hydroxyacetates,

oxydiacetic acid and oxydiacetates are interchangeably employed.

The cationic protein hydroxyacetates are prepared from Water insoluble proteins which are soluble in aqueous The preferred proteins are amphoteric water insoluble animal and vegetable proteins, of which casein and soybean protein are especially useful. The water insoluble globular proteins, the globulins and the glutelins, make up an important class of useful proteins, including the referred to soybean protein (principally glycinin), edestin' (from hemp seed), glutenin (from wheat) and orgenin (from rice).

In reacting a protein with hydroxyacetic acid, the amount of acid required for solution varies somewhat depending on the method of preparation and the age of the protein. Ordinarily, commercially available case in and soybean protein (sold as alpha protein, a product of high purity) are dissolved when sufficient acid is added to give a pH of about 4.2 to 4.7, and the pH is preferably brought to below about 4.4.

In preparing the new emulsions in accordance with the invention, the foregoing procedure for preparing cationic protein hydroxyacetate is followed until solution is complete, and then the substance to be emulsified is added, followed by intimate mixing of the composition. Commonly employed proportions of substance to be emulsified and protein are about -10 parts by weight of the former to 1 part of the latter. Thus, fat, oil, wax, resin and pigment emulsions are readily prepared, employing, for example, animal and vegetable tallow, castor oil, cocoanut oil, palm oil, hydrogenated fats and oils, spermacetti, stearine, Japan wax, paraffin wax, alkyd resins, petroleum resins, phenolic resins, hydroabietyl alcohol, or a pigment. At the same time, other ingredients, such as hygroscopic and foam-retarding salts, binders and lubricants, may be incorporated in the emulsions intended for use in sizing. Examples of salts that may be added are zinc and calcium chlorides and sulfates, and alkali metal acetates. Binders include such proteinaceous substances as albumin, glue, gelatin, and casein, and gums such as locust bean gum, karaya gum, gum tragasol, gum tragacanth, and gum arabic. On cooling, a gelatinous mass is obtained which may be stored for a considerable period of time, until it is desired to use it, for instance, by mixing it with a starch slurry for sizing yarn.

The new cationic protein hydroxyacetate emulsions are suitable for use in the older sizing processes, where an adhesive stiffener and a softener are mixed and heated together and then applied to the yarn. They are outstanding in their utility in homogenizer type of application to cellulosic and synthetic spun fibers, employing any of the several types of homogenizers used in textile plants for preparing size compositions, including votator and Manton-Gaulin as well as older types of homogenizers. Operation with a homogenizer involves heating and intimately mixing, e. g. by forcing through a small orifice, an aqueous mixture of an adhesive stiffener and an emulsion of a softener, most commonly a starch slurry and a fat or wax emulsion, after which the dispersion is charged to the size box for application to the yarn. The new emulsions are completely dispersible in the cold slurry, intimately and uniformly mixing with the starch. The adhesive stiifeners employed in the sizing processes include the aforementioned gums and such starches as potato, corn, wheat, rice, sago, sweet potato, tarina, and tapioca starches, and modified and converted starches.

Cationic protein hydroxyacetates are characterized by having. little or no tendency to foam, and emulsions prepared therewith produce correspondingly less foam. At the same time, the emulsions are eminently suited for admixture with the common defoaming and hygroscopic agents, previously referred to, care being taken to maintain the pH below about 7 toavoid breaking the emulsion. Also, hydroxyacetic acid will volatilize on drying, reducing the tendency of the-yarn to stick to the drying cylinders.

An outstanding result obtained by the use of the new emulsions. in warpsizing is that the amount of fat necessary fongood weaving is greatly reduced. For example,

it has been found that as little as one-third to one-half of the prior amount of fat is necessary when sizing with starch and cationic casein hydroxyacetate or cationic soybean protein hydroxyacetate emulsions. At the same time, it has been found that the resulting yarn is stronger, smoother, more flexible and better weaving, giving less clinging and shedding and higher weaving efficiencies in the weave room, even when the humidity is lowered considerably. These superior results apparently are due to much better dispersion and mixing with the starch than heretofore, resulting in greatly improved penetration and a more even and uniform sizing of the yarn. It appears that the latter. efit'ects are, in turn, .due to the cationic nature of the emulsions, giving rise to favorable electrical charge effects.

In preparing the new cationic protein emulsifying agents and emulsions, care should be taken that the acid employed is compatible with the yarn and with other components of the compositions. Thus, the reaction products of inorganic acids and proteins are not recommended for use with cellulosic fibers, on which the acids have a tenderizing elfect. The acid should also be volatilized on drying the yarns following application of the size composition.

The following examples, in which the parts are by weight, are given as illustrative .of the invention. It will be understood that the invention is not restricted to these exemplary compositions andimethods.

Example 1 900 parts of water and parts of casein or alpha protein are mixed with agitation, and about 10 to 33 parts of 75% aqueous hydroxyacetic acid (glycolic acid) are added to the mixture. The mixture is then heated with stirring to F. to 170 F. and maintained in that temperature range-until solution is complete. The amount of hydroxyacetic acid added depends on the type of casein employed, and is the amount necessary to produce a final solution pH of about 4.2 to 4.7, or the amount necessary to render solution complete. On cooling to room temperature (about 70 F. to 80 F.), gelatinous solid cationic casein hydroxyacetate or cationic soybean protein hydroxyacetate isobtained, which crumbles on stirring and which rapidly becomes liquid when heated to about 120 F.

Example 2 345 parts of water and 45 parts of casein are mixed with agitation, and 10 parts of 75% aqueous hydroxyacetic acid are added to the mixture. The mixture is then stirred and heated at -180 F. until solution is complete. While maintaining the temperature in the same range, 400 parts of beef tallow are added, and the mixture is stirred or put through a colloid mill until emulsification (oil-in-Water) is complete. On cooling to room temperature, a gelatinous solid is obtained.

The product can be mixed with a cold aqueous starch slurry in the preparation of a bath for sizing cotton, spun rayon, or filament rayon.

Example 3 360 parts of water and 45 parts of casein or alpha protein are mixed with agitation, and about 15 parts of 75 hydroxyacetic acid are added to the mixture. The mixture is then stirred and heated at 160 F. until solution is complete; While maintaining the temperature at 160-180 F., 400 parts of hydrogenated fish glycerides are added, and the mixture is stirred until smooth. 8-16 parts of zinc chloride (or an equivalent amount of zinc sulfate, calcium chloride or sulfate, or other foam-retarding salt), dissolved in a minimum amount of water, are then added. The mixture is diluted with tap Water to the desired percentage of fat, and it is put through a colloid mill to. complete emulsification, or is stirred until the temperature drops below about 110 P. On cooling to room temperature, a gelatinous fluid mass is obtained which is liquid when the fat content is below about onethird.

If desired, about 1 to 4 parts of locust bean gum, karaya gum, or similar binder may be added along with the zinc chloride, to furnish additional binding in a subsequent sizing operation.

Example 4 In the manner described in Example 2, a resin emulsion is prepared from 445 parts of water, 40 parts of casein, 15 parts of 75 hydroxyacetic acid, and 400 parts of a 50% solvent solution of a tall oil-resin modified phenolated alkyd resin (P-593 Beckosol solution).

Example 6 In the manner described in Example 2, a resin emulsion is prepared from 346 parts of water, 40 parts of casein, 6 parts of 75 hydroxyacetic acid, and 200 parts of a heat reactive, aromatic type, highly unsaturated liquid hydrocarbon petroleum residue resin (CTLA Polymer).

Example 7 In the manner described in Example 2, a pigment emulsion is prepared from 420 parts of water, 45 parts of casein, 10 parts of 75% hydroxyacetic acid, and 450 parts of a lead chromate pigment.

Example 8 In the mannerdescribed in Example 2, a titanium dioxide emulsion is prepared from 500 parts of water, 50 parts of casein, 15 parts of 75% hydroxyacetic acid, and 500 parts of titanium dioxide.

Example 9 In the manner described in Example 2, a resin emulsion is prepared from 150 parts of water, 10 parts of casein, 3 parts of 75 hydroxyacetic acid, and 70 parts of a pure phenolic resin (2100 Super Beckacite, manufactured by Reichhold Chemicals, Inc.) in 30 parts of xylol.

Example 10 In the manner described in Examples 49, cationic soybean protein hydroxyacetate emulsions of wax, resins, and pigments are prepared, employing sufficient hydroxyacetic acid to produce a soybean protein hydroxyacetate solution of pH below about 4.4.

Example 1 1 In a cotton weaving mill in Tennessee, an 80 x 80 cotton print cloth was slashed with the followingformula:

Pearl corn starch lbs l90 Cationic casein hydroxyacetate tallow emulsion, 25%

tallow content lbs 26 Water to finish gals l81 The tallow emulsion was prepared in the manner described in Example 3 from 279 parts of water, 12 parts of casein, 4 parts of 75% hydroxyacetic acid, 100 parts of beef tallow, and parts of zinc chloride. The emulsion was mixed with aqueous cold (about 70 F.) starch slurry, and the mixture was run into a votator where it was cooked under pressure at 290 F. for 4 minutes and then cooled to slightly below 212 F. The hot mix was discharged to a receiving tank at atmospheric pressure where it was held at 200 F. to 203 F. under agitation. Subsequently, the size composition was charged to the size box of the slasher. While maintaining the size bath 6 at 200 F. to 203 'F., the warp yarns were passed through the bath, after which they were dried and further processed in the usual manner.

Results were compared with those obtained employing, instead of the cationic casein hydroxyacetate tallow emulsion size mix containing 3.4% fat (based on the weight of starch), a size mix prepared with a mechanical fat mixture and containing 5% fat, previously used regularly in the mill as the preferred size mix. Loom efiiciencies determined in the plant as loom stops per loom hour in a set of 83 looms Were 0.19 for the casein hydroxyacetate fat emulsion treated yarn and 0.29 for the mechanical fat mixture treated yarn.

The usual speed in the slashers, Uxbridge hot air slashers, had been to 103 yards per minute. Without varying any condition affecting drying speed, the standard speed obtained with the yarn treated with casein hydroxyacetate fat emulsion was to 119 yards per minute. Thus, considerably accelerated production and lowered production costs resulted from the use of cationic casein hydroxyacetate fat emulsion.

Example 12 In South Carolina mills, cotton and spun rayon yarns were slashed in a manner similar to that described in Example 11, with the following formula:

Pearl corn starch lbs 280 Cationic alpha protein hydroxyacetate hydrogenated fish glycerides emulsion, 25% fat content lbs 28 Water to finish gals 314 The fat emulsion was prepared as described in Example 3. Preparation of the size mix, employing a votator, and further processing were carried out in the manner described in Example 11.

Example 13 In a Georgia mill, spun rayon yarn (50-50 viscose acetate blend) was slashed in a manner similar to that described in Example 11, with the following formula:

Thin boiling corn starch, 40 fluidity lbs Cationic alpha protein hydroxyacetate hydrogenated fish glycerides, emulsion, 25 fat content lbs 8 Water to finish gals The fat emulsion was prepared as described in Example 3. The size mix was prepared by cooking the ingredients at about the boiling point in a size kettle for about 1% hours. The cooked mix was charged to the size box of the slasher, and further processing was carried out in the manner described in Example 11.

Yarns were also sized in a number of other mills using cationic casein or alpha protein hydroxyacetate softener emulsion size mix containing 1% to 2% softener.

The results obtained in the plant operations carried out as described in Examples l1, l2 and 13 showed that with the use of cationic protein hydroxyacetate softener emulsion, the optimum amount of fat was reduced from 5% to 7%, employed previously, to 1 /2 to 3 /z% based on the weight of starch. Slashing speeds were increased, and no foam was in evidence in any of the operations. At the same time, stronger, smoother, more flexible, and better weaving yarn resulted, giving less clinging and shedding and appreciably higher Weaving efficiencies, even when the humidity was lowered considerably.

In the foregoing examples, oxydiacetic acid can be substituted for hydroxyacetic acid, employing about 7 parts by weight of the former in place of 10 parts of the latter.

The invention is not limited to the specific compositions and methods set forth, but numerous variations are possible within its scope.

I claim:

1. A warp sizing composition consisting essentially of an intimate mixture of water, an adhesive stifiener, selected from the group consisting of starches and gums and a softenerselectedfrom the group consisting of fats, oils andwaxes-emulsified with a cationic water insoluble, acid soluble protein salt with an acidcompatiblewithyarn and with the remainderof the composition.

2. A warp sizing composition consisting essentially of an intimate mixtureof Water, an adhesive stiffener, selected from the group consisting of starches and gums and a softener selected from the group consisting'of fats, oils and waxes emulsified with a cationic water insoluble, acid soluble protein selected from the group consisting of cationic hydroxyacetates and cationic oxydiacetates of a water insoluble, acid soluble protein.

3. The process for producing a warp sizing composition which consists essentiallyof intimately mixing water, an adhesive stiffener, selected from the group consisting of starches and'gurns and a softener selected from the group consisting of-fats, oils and waxes emulsified with a cationic water insoluble, acid soluble protein salt with an acid compatible with yarn and with the remainder of the composition.

4. The process for producinga warp sizing composi-- tion which consists essentially of intimately mixing Water, an adhesive stiffener, selected from the group consisting of starches and gums and a softener selected from the group consisting of fats, oils andwaxes emulsified With a cationic water insoluble, acid soluble protein selected from the groupconsisting of cationic hydroxyacetates and cationic oxydiacetates of a water insoluble, acid soluble protein.

5. In a process for warp sizing yarn, the step of immersing yarn in an intimate mixture of Water, an adhesive stiffener, selected from the group consisting of starches and gums and a softener selected from the group consisting of fats, oils and waxes emulsified with a cationic water insoluble, acid soluble protein salt with an acid compatible with yarn and with the remainder of the composition.

6. A warp sizing composition for yarn containing a fat emulsified with cationic casein hydroxyacetate.

7. A Warp sizing composition consisting essentially of an intimate mixture of Water, a starch, and a fat emulsified With cationic casein hydroxyacetate, the proportion of said fat being about 1% to 3 /2 based on the Weight of saidstarch.

8. In a process for warp sizing yarn with a composition including a fat, the improvement which comprises providing said fat in said composition in the form of an emulsion containing as an emulsifying agent, cationic casein hydroxyacetate.

9. In a process for warp sizing yarn, the step of immersing yarn in an intimate mixture of Water, a starch, and a fat emulsified with cationic casein hydroxyacetate.

10. A Warp sizing composition consisting essentially of an intimatemixture of Water, an adhesive stifiener, selected from the group consisting of starches and gums and a softener selected from the group consisting of fats, oils and Waxes emulsified with a cationic casein selected from the group consisting of cationic casein hydroxyacetates and cationic casein oxydiacetates, the proportion of said softener being about 5 to 10 parts by weight to 1 part of said casein.

11. A'warp sizing composition consisting essentially of an intimate mixture of=water, an adhesive stifiener, selected from the group consisting of starches'and gums and a softener selected from the group'consisting of fats, oils and waxes emulsified with a cationic soybean protein selected from the group consisting of cationic soybean protein hydroxyacetates and cationic soybean protein oxydiacetates, the proportion of said softener being about 5 to 10 parts by weight to 1 part of said soybean protein.

12. The process for producing a Warp sizing composition which consists essentially of intimately mixing water, an adhesive stiffener, selected from the group consisting of starches and gums and a softener selected from the group consisting of fats, oils'and waxes emulsified with a cationic casein selectedafrom the group consisting of cationic casein hydroxyacetates and cationic casein oxydiacetates.

13. The process for producing a warp sizing composition which consists essentially of intimately mixing water, an adhesive stiffener, selected from the group consisting of starches and gums and a softener selected from the group consisting of fats, oils and waxes emulsified with a cationic soybean protein selected from the group consisting of cationic soybean protein hydroxyacetates and cationic soybean protein oxydiacetates.

14. In a process for warp sizing yarn, the step of immersing yarn in an intimate mixture of Water, an adhesive stifiener, selected from the group consisting of starches and gums and a softener selected from the group consisting of fats, oils and waxes emulsified with a cationic casein selected from the group consisting of cationic casein hydroxyacetates and cationic caseinoxydiacetates.

15. In a process for Warp sizing yarn, the step of immersing yarn in an intimate mixture of water, an adhesive stifiener, selected from the group consisting of starches and gums and a softener selected from the group consisting of fats, oils and waxes emulsified with a cationic soybean protein selected from the group consisting of cationic soybean protein hydroxyacetates and cationic soybean protein oxydiacetates.

References Cited in the file of this patent UNITED STATES PATENTS 2,288,432 Billing June 30, 1942 2,342,739 Kratz Feb. 29, 1944 2,347,678 Gayer May 2, 1944 2,372,108 Neher Mar. 20, 1945 2,410,382 Kaplan Oct. 29, 1946 2,413,501 Huppert Dec. 31, 1946 2,559,848 Caldwell July 10, 1951 2,639,235 Kennedy et al May 19, 1953 2,682,469 Stuart et al. June 29, 1954 OTHER REFERENCES Vilenskii et al. in ChemicalAbstracts, vol. 34, of 1940, page 2681. 

10. A WARP SIZING COMPOSITION CONSISTING ESSENTIALLY OF AN INTIMATE MIXTURE OF WATER, AN ADHESIVE STIFFENER, SELECTED FROM THE GROUP CONSISTING OF STARCHES AND GUMS AND A SOFTENER SELECTED FROM THE GROUP CONSISTING OF FATS, OILS AND WAXES EMULSIFIED WITH A CATIONIC CASEIN SELECTED FROM THE GROUP CONSISTING OF CATIONIC CASEIN HYDROXYACETATES AND CATIONIC CASEIN OXYDIACETATES, THE PROPORTION OF SAID SOFTENER BEING ABOUT 5 TO 10 PARTS BY WEIGHT TO 1 PART OF SAID CASEIN. 